Detergent additives



United States Patent 1m 1 2,982,739" r DETERGENT ADDITIYES Vladimir Dvorkovitz, Kansas City, Mo., and Neil'W. Berst and George G. Leist, Evanston, Ill., assignors to The Diversey Corporation, a corporation of Illinois I No Drawing. Filed July 15, 1955, Ser'. No. 522,369 1 2 Claims. or. 252-156 This invention relates to additives that reduce the skin irritation that is normally .associated with the use of detergent formulations, the commercial application of said additives and detergent formulations containing said additivesm" a We have discovered that when water-soluble salts and/or water-soluble acids of hydroxy carboxylic acid derivatives having a total of at least 3 of the radicals: hydroxyl and carboxyl, as'well as materials-that form said salts and/or acids upon hydration, are combined with detergents or detergent solutions (i.e., aqueous'solutions, 'etc.), they tend to reduce the skin irritation that 'is normally associated with detergent formulations. These materials shall herein be referred to as additive(s). For example, materials such as gluconic acid or glucono delta-lactone (forms gluconic acid upon hydration), tartaric'acid and citric acid, as well as salts of said acids '(i.e., amine salts, alkali metal salts, ammonium salts) tend to inhibit the irritating effect on; skin that is normally induced by detergent formulations; f'

The additives, as well as combinations of the additives,

are particularly effective when used in conjunction with alkaline detergents; however, they may also be employed *with substantially neutral detergents as well as detergent formulations 'containing niixtures of alkaline detergent (s) plus substantially neutral detergent(s).

. The additives may be employedwith alkaline deterlgents such as phosphates, complexlphosphates, silicates,

soda ash, caustic, borates and the like which may contain alkali metal, amine and ammonium substituents.

The term substantially neutral detergents includes One of the conventional methods of studying skin irritation is to intradermally inject 0.5 cc. of the detergent formulation being tested into freshly'shaved American chinchilla rabbits. Observations are made after 24 hours and readings are made on the basis of 0 (for no irritation) to 5 (for very bad irritation).

Tests were first started using malechinchilla rabbits for test animals in accordance with the above-mentioned conventional test procedure. It was found, however, that about /3 to about /2 of the test rabbits had large, dark pigmented areas of skin that made the interpretation of results diflicult. Male albino rabbits were then obtained and a series of conventional tests were made with both types of rabbits to determine if the same results, or at least the same relative .results would be obtained with either kind of rabbit. The results of these comparison tests are shown in Table'I. A series of raw materials common to detergent formulations were injected at concentrations or V2 ounce per gallon with an injection pat tern reading from the back of the rabbit to. the front:

2 4 6 8 where 1-2 were saline solution controls, 3-4, 5-6 and 7-8 were duplicate injections of three raw materials (eg.,

3-4 were tetrasodium pyrophosphate; 5-6 were TABLE I Comparison of results obtained with male American chinchilla rabbits and male 'albino rabbits Rating of Irritation on Rabbits Chinehlllas Name of Materlal (Soln. at OzJGal.)

Alblnos Tetrasodium Pyrophosphate Tris odium Phosphate, Flnes Trip olyphosphate Soda Ash Niter Cake Oronite D60 Sodium Gluconat Triton X- In subsequent tests, our procedure consisted of injecting 0.5 ml. of solution intradermally into the side of a freshly clipped male albino rabbit. It was found that by carefully clipping the rabbits it'w'as not necessary to shave the small amount of remaining hair. By wetting 'the area with alcohol, injections and'observations were easily made. Tests were usually made at concentrations of M4, /2 and 1 ounce per gallon; these concentrations gave a degree of irritation that was definite, but not excessive. Eight injections were made to one rabbit side, and

a replicate test was made inmost cases on another rabbit.

Observations were made after. 24 hours and ratings were given on the basis of a scalewherein 0 represents no irritation and 5 represents verynbad or maximumirritation. The effect of, an additive on the detergents'was best detected when the detergent alone (without the additive) had a rating of 2 to 3. I I

The tests tabulated in Tables II-VIII were made on albino rabbits. Additives of various concentrations were employed. The concentration of the detergent formulations were 4 ounce per gallon, /2 ounce per gallon and 1 ounce per gallon. Replicates were run in most tests.

The injection pattern was from back to front:

where 1-2 were saline controls, 3-5-7 were injections wherein one concentration of the detergent was used, }4-6-8 were tests wherein the concentration of the detergent was the same as 3-5-7 and the concentrations of the additive were successively increased. Thus, injections 3-5-7 were identical control injections of detergent for the three different concentrations of additive employed-in injections 4-6-8. The concentration of the additives in the tables is based upon the total solids in the detergent plus additive compositions.

Tables II-IV show the results of testing glucono deltalactone, tartaric acid and citric acid additives, respectively, in conjunction with solutions of detergents such as sodium metasilicate, soda ash, trisodium phosphate, Triton X-100, and Oronite D-60. The results of these tests is givenas to degree of irritation and data is presented in the form of Treated Result and Untreated Result (e.g., 3-4 shows that the average degree of irritation with the indicated additive is 3 as compared with 4 for the detergent solution without the additive).

Since Orom'te D-60 is only about 60% active, the solutions were made 100% active at theindicated concentrations (oz/gal.) in each of the subsequent tables.

TABLE II Summary of the efiect of glueono delta-lactone on reducmg skin irritation caused by various detergent components Concentration Component Causing Irritation Degree of of Glucono Irritation, delta lactone, Treated- Percent of Conc., Oz./ Untreated,

Solids Name Gal. 24 Hrs. after Injection 2. Sodium Metasilicate 1 3.5-4 4. 0...- 1 3.5-4 9 d 1 3. 5-4 2. 0. 5 v 1. 5-3 4. 0.5 1. 5-3 9. 0. 5 1. 5-3 1. 0. 5 2. 5-3. 5 0. 0.5 2-3. 5 0. 0. 5 2. 5-3. 5 2.44 0. 25 0.5-1.5 4.76 0. 25 0.5-1.5 9.1. 0. 25 0. 5-1. 5 2.44 1 2.5-3.5 4.76 1 2. 5-3. 5 9.1- 1 2-3. 5 2.44 0.5 0-1. 5 4.76 0. 5 0.5-1.5 9.1.. O. 5 1-1. 5 1.0.. 0. 5 1-2 0.5.. 0.5 1-2 0.1.. 0.5 1-2 2.44 1 2-3 4.76 1 2-3 0.1. l 1. 5-3 2.44 0. 5 l-2 4.76 0.5 0. 5-2 9.1- 0.5 0. 5-2 2.44 1 2-3 4.76 1 2-3 9.1.. 1 2-3 2.44 0.5 0-0. 5 0.1- 0. 5 1-1. 5 2.44 l 1. 5-2 4.76 1 1-2 9.1- 1 1-2 2.44 0. 5 0. 5-1 1.0- 0.5 1-1. 5 0.5- 0. 5 1-1. 5 0 0.5 0. 5-1

TABLE III Summary of the efiect of tartaric acid on reducing skin Irritation caused by various detergent Components Component Causing Irritation Degree of Concentration Irritation, of Tartarie Treated- Acid, Percent Conc., Untreated, of Solids Name Oz./Ga1. 24 Hrs. After Injection 6.25. Sodium Metasi1icate.-- 0. 25 2. 5-8 11.8.- -.--.d0 0. 25 2.5-3 21.1 .d 0.25 2.5-3 1.64-- Soda Ash. 1 3. 5-5 3.23-. do..... 1 2.5-5 6.25-- (10.. 1 1. 5-5 3.23.. '.d().. 0.5 0. 5-2 6.25 -;do.- 0.5 0.5-2 11.8 --d0-- 0. 5 0. 5-2 6.25 .do.. 0. 25 0-1. 5 11.8 -60-- 0. 25 0-1. 5 21.1 "do 0.25 0-1. 5

- TABLE IV Summary of the efiect of citric acid on reducing Skill irritation caused by var ous detergent components Component Causing Irritation Degree of Concentration Irritation, of Citric Acid, Treated- Percent of Conc., Untreated,

Solids Name Oz./ Gal. 24 Hrs. After Injection 6.25 Sodium Metasilicate..... 0. 25 1-2 11.8-- -.-.-do 0. 25 1-2 21.1-- 0. 25 1-2 1.64.- 1 2. 5-4 3.23.- 1 2. 5-4 6.25.. 1 2-4 3.23.- 0. 5 0-1 6.25-- 0. 5 0-1 11.8 0. 5 0-1 Tables V and VI show the results of tests with lecithin and cetyl alcohol-urea complex, respectively; these materials were used as a basis for comparing their efiectivemess with our additives. The cetyl alcohol-urea complex is described in US. Patent 2,675,356. Lecithin was used since it has been alleged'that the presence of" 0.005 to 0.1% of soybean lecithin in detergent solutions protects the cell membranes against the irritating action of the detergent.

TABLE V Summary of the efiect of lecithin on reducing skin irritz'ztion caused by various detergent components Component Causing Irritation Degree of Concentration Irritation, of Lecithin; Treated- Percent of Conc., Untreated,

Solids F Name Oz./Gal. 24 Hrs. After Injection 1.24 Sodium Metasi1icate.-.. 1 '4. 5-4. 5 2.44. do 1 4-4 4.76. 1 4-4 9.1... 1 4-4 1.24. 0. 5 1. 5-2. 5 2.44. 0. 5 2. 5-3 4.76- 0. 5 2. 5-3 9.1... 0.5 3-3. 5 1.24. 0. 25 1-1. 5 2.44- 0. 25 1-2 4.76. 0. 25 1. 5-2 9.1.. 0. 25 2-2 1.24.- 1 3- .5 2 44 1 3-3. 5 4.76 1 3-3. 5 1.24 0.5 1-2 2.4 0.5 1-2 4.7, 0.5 1.5-2 1.24- 0. 25 0- .5 2.44- 0. 25 0-0. 5 4.76' 0. 25 0-0. 5

TABLE VI Summary ofthe effect of cetyl alcohol-urea .complex on reducing skin irritation caused by various detergent components Concentration Component Causing Irritation Degree of of Cetyi Alco- Irritation, hol-Urea Com- Treatedplex, Percent Conc., 0z./ Unrteated,

of Solids Name Gal. 24 Hrs. After Injection 1.24... 1 2.4 1 4-4 4.76. 1 4-4 1.24. 0. 5 2-3 2.44- 0. 5 2. 5-3 4.76. 0. 5 3-3 1.24- 0. 25 0. 5-0. 5 2.44. 0. 25 0. 5-0. 5 4.76. 0. 25 0. 5-0. 5 1.24. 1 1-3 2.44- V 1 2-3 4.76- 1 2. 5-3 124. 0.5 0.5-1.5 2.44- 0. 5 1-1. 5 4.76 0. 5 1-1. 5 1.24; 0. 25 0-0. 5 2.44. 0. 25 0-0. 5 4.76- 0. 25 0-0. 5 2.44- 1 l-2 4.76. 1 1-2 9.1-. 1 1-2 2.4 0. 5 0. 5-1 4.76 0. 5 0. 5-1 9 1 V 0. 5 0. 5-1 2.44 0. 25 0. 5-0. 5 4.76 0. 25 0.5-0. 5 9.1 0. 25 0.5-0. 5

The data shown in Table VII indicates that sodiu n gluconate, tartrate and citrate are effective additives.

TABLE vn Oz./Gal. Concentration of Metasilicate Cone. of Oz./Gal. 1 z./Gal. Name of Addition Addition, Replicate 1 Replicate 2 2 Percent of total Solids Replicate 1 Replicate 2 Replicate 1 Replicate 2 With- With With- With With- With With- With With- With With- With out out out out out out 9.1 a 0 3 i 0 4 s 5 1 4. 76 3 3 3 1. 5 4 3 5 2. 5 2. 44 3 2 3 3 4 3 5 1 11. 8 4 1 3. 5 2 6. 4 2 3. 5 2 5 4 5 4 3. 23 4 2 3. 5 2. 5 5 4 5 4 Concentration of Soda Ash Table VIII shows the effect in various additives upon various compositions that contain more than 1 detergent product.

TABLE VIII Efiect of additives of reducing skin irritation caused by various detergent formulations Reaction at 1 Oz./Gal. of Gene Formulated Product of Additive Additive Pef- Replicate 1 Replicate 2 can I Total Solids With- With With- With out out FORMULATION XF-iOO 1 Glucono delta-lactone 9.1 2 1. 5 2 0.5 4. 76 2 1 2 0. 5 Glucono delta-lactone 2.44 2 0. 5 2 0 Cetyl Alcohol-Urea Complex.... 9. 1 0 0 2 1. 5 Cetyl Alcohol-Urea Oomplex 4. 76 0 0 2 1 Oetyl Alcohol-Urea Complex.... 2. 44 0 0 2 1 FORMULATION XF-200 I Glucono delta-lactone 9. 1 2 0 0 0 Glucono delta-laetone--- 4. 76 2 0 0- 0 Glucono delta -laetone; 2. 44 2 1 I 0 I 0 Oetyl Alcohol-Urea Oomplex 9. 1 1. 5 O 2 2 I Oetyl Alcohol-Urea 0omplex 4.76 1. 5, 0. 5 2 1 Oetyl Alcohol-Urea0ompleL 2. 44 I 1. 5 0 I 2 1 SURF l Urea Urea The additives (i.e., glucono delta-lactone) have been shown to be eifective when employed with the detergent in quantities as low as about 0.1% by weight (based upon the weight of the total solids in the detergent plus additive compositions) as shown in Table H, but we do not limit the invention to this concentration, although in order to insure the most efiective results we prefer not to use less If desired, higher concentrations of the additive may be employed.

Although the present invention has been described in conjunction with preferred embodiments, it is to be'understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the invention and appended claims.

We claim: 1. A nonacid detergent composition having an additive which reduces the skin irritation that is normally induced by nonacid detergent compositions, said composition con- I sisting essentially of: a synthetic organic detergent from the group consisting of sodium-higher alkylbenzenevsulfonates and higher alkyl phenyl'ethers of polyethylene glycol, and at least 0.1% by weight, based on total solids, of a water-soluble additive which reduces the Skininita tion normally induced "by said organic detergents, said additive being a member from the group consisting of gluconic acid and water-soluble alkali metal salts thereof,

1 See following table: I by weight Soda Ash I 54.77.. Sodium tripolyphosphate 28.

l aryl sulio 15.00 Octyl phenol polyoxyethylene ether 2. 00 I Sodium carhorymethylcellulose..- I 0. 23 I Bee following table: I I j Sodium tripolyphosph n I I 22. 00 Sodium metasilim I I 16.00 Sodium carboxymethylcelluiosa 0.23 SodaAsh I I I 58.27 Sodium dodecyl benzene sulionate..... 2. 80 .1 Ethylene Glycol 0. 7!) ate said synthetic organic detergent being present in saidcomposition" in an amount in excess ofsaid additive.

2. He composition of claim 1 which includes an alkaline inorganic detergent -which serves as a detergent builder. I

I References Cited in thefilefof this patent I UNITED STAT ES PATENTS I oreatnr 'it i utn mgn Oct. 27, 1937 

1. A NONACID DETERGENT COMPOSITION HAVING AN ADDITIVE WHICH REDUCES THE SKIN IRRITATION THAT IS NORMALLY INDUCED BY NONACID DETERGENT COMPOSITIONS, SAID COMPOSITION CONSISTING ESSENTIALLY OF: A SYNTHETIC ORGANIC DETERGENT FROM THE GROUP CONSISTING OF SODIUM HIGHER ALKYLBENZENE SULFONATES AND HIGHER ALKYL PHENYL ETHERS OF POLYETHYLENE GLYCOL, AND AT LEAST 0.1% BY WEIGHT, BASED ON TOTAL SOLIDS, OF A WATER-SOLUBLE ADDITIVE WHICH REDUCES THE SKIN IRRITATION NORMALLY INDUCED BY SAID ORGANIC DETERGENTS, SAID ADDITIVE BEING A MEMBER FROM THE GROUP CONSISTING OF GLUCONIC ACID AND WATER-SOLUBLE ALKALI METAL SALTS THEREOF, SAID SYNTHETIC ORGANIC DETERGENT BEING PRESENT IN SAID COMPOSITION IN AN AMOUNT IN EXCESS OF SAID ADDITIVE.
 2. THE COMPOSITION OF CLAIM 1 WHICH INCLUDES AN ALKALINE INORGANIC DETERGENT WHICH SERVES AS A DETERGENT BUILDER. 